Conversion process and apparatus



June 18, 1963 Filed Feb. 7,

M. P. swEENEY 3,094,479

CONVERSION PROCESS AND APPARATUS 2 Sheets-Sheet 1 Mmc@ ALA/m4.

June 18, 1963 l M. P. SWEENEY 3,094,479

l CONVERSION PROCESS AND APPARATUS Filed Feb. 7, 1958 2 Sheets-Sheet. 2

INVENTOR.

BY /7/'5 affomeys /6402414 aan@ M nite tates 3,694,479 CNVERSlN PRCESSAND APPARATUS Maxwell Patrick Sweeney, Philadelphia, Pa. (2341/2 S.Bonnie Brac St., Los Angeles 57, Calif.) Fiied Feb. 7, 1953, er. No.713,363 4 Claims. (Cl. 2tlg-76) verting lower value hydrocarbons such asmethane,

ethane, propane, butane or petroleum oils. These same raw materials canalso be used to make Fischer-Tropsch synthesis gas (CO-l-Hg), andammonia synthesis gas (HH-N2) in processes which involve a pyrolysisstep. Waste materials, such for example as sulphite base waste liquorfrom pulp mills, are also treated by methods employing pyrolysis.

A great variety of different techniques have been suggested for carryingout these pyrolysis processes. In recent years, for example, muchattention has been given to the fluidized bed technique, in which thehydrocarbon to be converted is sprayed into a mass of hot fluidizedsolids, and thereby pyrolyzed. This technique is satis- -factory forcertain applications, but involves large plants which are expensive tobuild and operate. Moreover, there is a minimum contact time in suchbeds which cannot be lessened and when products such as acetylene aredesired, this time is too long, because the acetylene will Igoliymerizeor decompose before it can be taken from the To achieve a shortercontact time it has been proposed to inject the hydrocarbonaceousmaterial to be pyrolysed into a ame, followed by sudden quenching withwater. Maintaining a flame in a reducing atmosphere converts the carbonburn-ed mainly to CO instead of CO2, thus giving less than one third asmuch heat, fails to burn much of the hydrogen, burns some of the desiredproduct, and completely wastes the large amount of sensible heat in theproduct gases; thus, this is an expensive technique using largequantities of fuel and the gaseous products are always greatlycontaminated with carbon oxides, and With nitrogen if air is used as theoxidizing medium.

It is an object of the present invention to provide a process for theconversion of low value hydrocarbonaceous material which is moreeconomical to operate than existing systems.

It is another object of the invention to provide an apparatus of theclass described rwhich is smaller and less expensive to build andoperate than existing systems.

It is another object of the invention to provide a method and apparatusfor the pyrolysis of hydrocarbonaceous materials which can be used toprovide valuable unsaturated compounds in which contamination bynitrogen or oxides of carbon is minimized.

It is another object of the invention to provide a method and apparatusfor the pyrolysis of hydrocarbonaceous materials in which the reactiontime can be varied from extended to very brief periods.

It is a further object of the invention to provide a method forremoving, and thus preventing excessive build up of solid depositsformed during a pyrolysis process at or near the pyrolysis Zone.

lt is a further object of `the invention to provide an economical methodfor rapidly quenching products of high temperature pyrolysis.

3,094,479 Patented .lune 18, 1963 In accordance with a principal aspectof the invention, t'hese and other objects are attained by passing thehydrocarbonaceous material to be pyrolysed through a mass of fibrousheat exchange or heat storage material, :at least a portion of said heatexchange material being at a temperature suicient to cause pyrolysis ofthe hydrocarbonaceous material. Preferably, the mass of heat exchangematerial is passed in a circuitous path which includes a pyrolysis Zoneand a reheating zone. Hydrocarbonaceous feed is passed through the heatstorage material .in the pyrolysis zone and is heated and therebypyrolysed to give vaporous products, which are at least partially cooledby the heat storage material, and a nonvaporous residue which remains onthe heat storage material. The heat storage material is then removedfrom the pyrolysis zone to the reheating Zone where it is brought intoContact with oxygen. By this means the residue is burned od and the heatexchange material is at least partially reheated.

In a preferred arrangement the fibrous heat storage mateiial is arrangedin an annular mass and rotated about an axis. Hydroca-rbonaceous feed iscontinuously passed through one section of the mass and pyrolysed andair, or other oxygen containing gas, is continuously passed throughanother section to burn off pyrolysis residue thereby partiallyreheating the heat storage material. Additional fuel may also be addedto the air to furnish the remainder of the heat required.

If desired, the vaporous products of pyrolysis removed from thepyrolysis section may be passed through a quenching section wherefurther pyrolytic decomposition is arrested.

The composition of the fibrous heat exchange or heat storage materialused will depend on the particular reaction being conducted. For lowtemperature pyrolysis, i.e. below about 1200 F. materials such as glassWool, asbestos, or metallic Wires may be used. Preferably, however, andparticularly where the temperatures involved are above about 1200 F.,aluminum silicate fibers, such as those manufactured by the CarborundumCompany and sold under the triade name Fiberfrax are employed. Recentlygraphitic -fibers have been developed and these may also be used in`certain embodiments, or if they are properly treated to becomenon-oxidizable.

The physical form of Athe apparatus employed may vary from oneapplication to another. Basically the preferred apparatus consists of anannular container having perforated walls and divided into sections byradial partitions. The sections are lilled with heat exchange material.Means are provided for introducing feed into and removing product fromone set of sections, for passing oxygen or an oxygen containing gasthrough another set of sections and for rotating the annular containerabout its axis.

The hydrocarbonaceous feed employed in the present invention may bedrawn from a wide variety of materials including gases such as methane,ethane, propane and butane and liquids such as recycle gas oil, bunker Cfuel oil, coke oven tar, low .temperature coal carbonization tar, andwaste sulphite liquor. Solids such as coal, lignite or peat may also beused; however, here serious practical diculties are encountered and theadvantages of the invention are less attractive. As used the feed mustbe iiuidized. lf it is a liquid it is preferably either vaporized beforebeing brought into contact with the hbrous material, evenly sprayed onthe fibrous material, or is dispersed in some innocuous carrying gassuch las steam or nitrogen. Solids must be gasiform, e.g. iin-elydivided :and entrained in a carrying gas, in a disperse phase beforeintroduction or dissolved in a recycle oil or the like.

As noted, the process can be applied to a number of different pyrol-ysisreactions. Some of the most important are:

(l) Conversion of methane to acetylene;

(2) Conversion of butane and propane to acetylene,

ethylene, butylene and butadiene;

(3) Conversion of methane to Fischer-Tropisch synthesis sas;

(4) Conversion of methane to ammonia synthesis gas;

() Conversion of methane, ethane, propane, or butane to aromatics;

(6) Conversion of heavy oils (eg. bunker C fuel oil) to various productsincluding acetylene, butadiene, and aromatics;

(7) Recovery of SO2 and NH3 from ammonia base waste sulphite liquor.

The conversion of various hydrocarbons to acetylene is of particularinterest because the use of the novel technique permits extremely shortreaction times at high temperatures, ie. as low as about 0.001 second,to be obtained, thus preventing destruction of the acetylene Ias it isproduced.

The invention will be further described with reference to theaccompanying drawing in which:

FIG. l is a view, partly in elevation and partly in vertical section(along the line 1--1 of FIG. 2) of a pyrolysis unit for use with thepresent invention.

FIG. 2 is a View in horizontal section of the unit of FIG. l, takenalong the line 2 2 of lFIG. 1.

FIG. 3 is a perspective View showing the construction of the rotor ofFIGS. 1 and 2.

FIG. 4 is a View in vertical section of a modified form of ra pyrolysisunit according to the invention, especially adapted for processingliquid feeds.

FIG. 5 is a View in vertical section taken along the line 5--5 of FIG.4.

FIG. 6 is a view in vertical section of still another form of theinvention, suitable for use in processes where there is a liquid feed orin processes where a somewhat larger contact time is desired.

FIG. 7 is a view in horizontal section along the line 7-7 of FIG. 6.

Referring first to FIG. l, a pyrolysis unit according to the inventioncomprises a shell 1, enclosing a casing 2. The shell 41, which may be ofsheet steel or other structural material, supports a motor 3 having ashaft 4 which extends downwardly through the casing 2. A stuffing box 5is provided on topi of the casing -2 to furnish a gastiglrt seal andjournal for the shaft 4. Suspended from the bottom of shaft 4 is a rotorindicated generally as 6. The rotor 6 comprises an upper plate 7 whichis formed of a sheet of structural material such as steel 7a 'and alower sheet 7b of insulating material such for example as magnesite. Itsouter edge 8 is provided with a sealing surface such for example asgraphite for reasons which will become apparent. Attached to the lowersurface of the plate 7 is an annular chamber indicated generally as 9.This cham-ber 9 is formed by two perforated Walls 10 and 11. These wallsmay be formed of perforated silicon carbide plates or heat resistantmetal screening; for example, screening made of a high temperature alloysuch as one composed of 94% nickel, 3% manganese, 2% aluminum, and 1%silicon. The chamber is divided into a number of sections 12-23 byradial walls 24. Each section is filled with a fibrous heat exchange orheat storage material such, for example, as Fiberfrax The walls 24 maybe made from Carlborundum or from a heat resistant alloy and the fibrousmaterial may simply be placed at nandom in the spaces between the walls.Alternatively, and this is preferred where a substantial pressuredifferent exists from one section to another, the fibrous material isused in the form of a web or blanket which is wrapped around the innerWall 10. The walls 24 are built upy during the wrapping of the fibrousmaterial by spraying the material with a temperature-resistant adhesiveat each point where it is desired to form the Walls 24.

In some instances, where the fibrous material has substantial structuralstrength the inner wall 10 of the annular chamber 9 may be eliminated.

At the bottom of the chamber 9 a sealing ring 25 is secured. Thisprovides a sealing surface for the lower section of the rotor. Beneaththe rotor is a base block 26 formed of some refractory material such asfire brick or magnesite. A stationary sealing ring 26a is provided onthe upper corner of the block 26 for cooperation with the sealing ring25 of the rotor 9. The base block 26 has extending upwardly from it asealing divider 27. The divider 27 is `again made of `a refractorymaterial such as silicon carbide and has at its extremities sealingshoes 2S and 29. It divides the inside space into two zones 44 and 45.The casing 2 is `further provided with an upper sealing ring 30 having acircular shoe 31 which extends around the rotor and cooperates with thesurface 8 on the upper plate of the rotor. Vertical sealing legs 32-35are provided on the casing 2. These legs are also provided with sealingshoes 36-39 which are in close cooperation with the outer wall 11 of therotor. They divide the annular space between the inner casing 2 and therotor into 4 compartments as will be noted from FIG. 2. A duct 40 isprovided emptying into the annular space bounded by the casing 2, theouter wall 11 of the rotor, the vertical sealing legs 34 and 35, -base46, and the upper sealing ring 30. Another duct 41 is providedconnecting into the space defined by the casing 2, the outer wall 11 ofthe rotor, the vertical sealing legs 33 and 34, base 46, and the uppersealing ring 30. A third duct 42 is provided connec-ting with the spacedefined by the casing 2, the outer wall 11 of the rotor, the verticalsealing legs 33 land 32, base 46, and the upper sealing ring 30. Afourth duct 43 is provided connecting with the space defined by thecasing 2, the outer wall 11 of the rotor, the vertical sealing legs 32and 35, base 46, and the upper sealing ring 30.

In operation, the motor 3 is energized and causes the rotor 9 to rotateon its axis. Hydrocarbonaceous material to be pyrolysed is introducedthrough the duct 40. It flows into the casing 2 and then through theholes in the outer wall 11 of the rotor. The fibrous material in thesections 17-13, as will later appear, is hot from previous treatmentsand at least at the inner surface is at a temperature sufficient tocause pyrolysis of the hydrocarbon. The hydrocarbon flows through thefibrous material and is pyrolysed to form vaporous products and aresidue which may consist of carbon, tars, and other heavy material. Thevaporous product iows into the central chamber 44 while the residueremains on the fibrous material. Pyrolysis continues in chamber 44. Fromthe chamber 44 the yvaporous product flows radially outwardly throughthe sections 15-16 where it is rapidly cooled to a temperature belowthat at which it would be fur-ther decomposed and normally toatempera-ture somewhat above the inlet temperature in duct 40. Thecooled product flows into the space between the rotor and the casing andis thence removed from the unit through duct 41.

At the same time that hydrocarbonaceous feed i-s introduced through duct40, an oxygen-containing gas such as air is introduced through the duct42. It iiows through the space between the rotor and the casing 2 andthence through the sections 23, 12, 13, and 14. Here is burns thepyrolysis residue from the fibrous heat exchange material, heating upthe material. The hot products of combustion still containing excess airilow into the central chamber 45, wherein auxiliary fuel is introducedthrough nozzle 47, which burns with at least a portion of the excessair. The products of combustion then ow radially outwardly through thesections 21, 22, '20 and 19, where additional combustion occurs withconcomitant heating. The products of combustion flow through the spacelbetween the rotor and the inner chamber and are removed through duct43. Considering the same operation from the standpoint of the matrix offibrous heat exchange material it will leave the reheating Zone whichpoint, assuming that the rotor is moved counter-cloclcwisc (see FIG. 2),is indicated by the vertical sealing leg 35, at an inner temperaturewhich is dependent upon the amount of combustion that has been carriedout but which will normally be on the order of 1600 F. to 3000 F., andan outer temperature normally on the order of 150 F. to 500 F. A radialtemperature gradient between these end temperatures will exist withinthe intermediate zones of the matrix. As it moves away from the sealingleg 34 it is met with fresh hydrocarbonaceous feed at a temperature ofsay 50 F. to 700 F. This will cause cooling of the fiber matrix andheating of the hydrocanbonaceous feed so that by the time the matrix hasreached the vertical sealing leg 35 its peripheral portion "willapproach closely the temperature of the fresh feed.

The inner portion on the other hand will be at the temperature requiredto pyrolyse the feed. As the matrix passesxbeyond the vertical sealingleg 34 it receives hot products of pyrolysis from the central chamber44. 'Ihese products -ow through the matrix and upon emerging from theperipheral portion of the matrix are somewhat above the temperature ofthe feed introduced through duct 40. As the ber moves toward thetvertical sealing leg 33 the temperature of its peripheral portionincreases. This increase, however, is not suicient .to causedecomposition or recombination of the products of pyrolysis. As it movespast the vertical `sealing leg 33 the liber is met Iby air which may bepreheated in an external apparatus (not shown), if desired, say to 600F. In any case, the pyrolysis residue is burned off. The tempera-ture ofthe inner fibers increases to say l500 F. to 2500 F. by the time thematrix reaches the vertical sealing leg 32. In between sealing legs 32and 35 the inner fibers increase in temperature still further, normallyto about 1600 F. to 3000 F., and the outer fibers will also increase intemperature, usually to about 150 F. to 600 F.

The embodiment of FIGS. 1-3 is preferred for situations where thehydrocarbonaceous feed is gaseous. A somewhat different embodiment ispreferred for a liquid feed, and a system which is particularly valuablein the pyrolysis of waste sulphite liquor is shown in FIGS. and 5. `Inthe embodiment of FIGS. 4 and 5 the rotor 1s moved about a horizontalrather than a vertical axis and the feed is introduced through a seriesof pipes in the center of the rotor. Referring specifically to FIGS. 4and 5, the pyrolysis unit shown there comprises a casing 100 having aninlet duct 101 in its top and an outlet duct 102 at the bottom. Insideand disposed about the periphery of the casing 100, at one end thereofIis a sealing ring 103. A similar ring 104 is located at the oppositeend. An end wall 105 of the casing is provided with a stuliing box 106adapted to receive a shaft such as 107 driven by a motor 107:1. At theopposite end of the casing there is provided a bearing block S havingshoulders 109 and 110 and insulation 128. A duct 111 with internalinsulation (not shown), is provided in the block and the block is alsoprovided with an aperture to receive a row of spray pipes 112. Thesespray pipes are welded together to provide a gas impermeable surface andare fitted with sealing shoes 113 and 114 (FIG. 5). Inside the casingthere is mounted a rotor 115. This rotor is of the general typedescribed above in connection with FIGS. 1-3 and comprises a series ofsections 116 defined by radial partitions 117 and filled with fibrousheat storage material. As 4in the embodiment of FIGS. 1-3 the walls ofthe rotor may be made of perforated silicon carbide plates or somealloyed metal. The partitions 117 may be made of a similar material ormay be `built up by a temperature resistant adhesive being applied tosucceeding courses of fibrous material along axial lines, therebyforming radial partitions. The rotor 115 has end walls 118 and 119 whichare separated from the high temperature zone by insulation 129. Theinner corners of these walls, as indicated at 120 `and 121, and theirouter edges 122-125 are provided with bearing surfaces for providing amoving contact with the bearing rings 103 and 104 and the bearingsurfaces of the block 108. In operation, a liquid hydrocarbonaceousfeed, such as waste sulphite liquor is introduced through pipe 126 andmanifold 127 and flows through the spray pipes 112. It is sprayed intothe interior of the rotor 115 and comes against the lower interiorsurface of the rotor. This surface is extremely hot, having previouslybeen contacted with hot products of combustion. 'Ihe liquor is thereforevaporized to give steam, sulphur gases, ammonia and oily products whichare removed through the duct 102. As the rotor is revolved by the shaft117 and comes into the upper half of the pyrolysis unit, lair, a mixtureof air and fuel, or a mix-ture of air (or oxygen), and hot products ofcombustion formed in an external burner (not shown), is introducedthrough duct 101 and moves downwardly through the mass of fibrousmaterial. The oxygen in these gases burns off the pyrolysis residueformed in the lower portion of the unit. It heats the fibrous materialto say 1200 F. to 2500 F., at its hottest zone. The resulting productsof combustion are removed through duct 111.

FIGS. 6 and 7 show a further modification of the invention which is alsosuitable for use with liquid feeds as well as with processes where asomewhat longer contact time is desirable.

The embodiment of FIGS. 6 and 7 comprises a casing 200 supported by legs201. The casing has a cylindrical side wall 202, a cover 203 and a floor204. A motor 205 is located beneath the floor 204 and has `a shaft 206extending up through the floor. A stuiiing box 20651 provides agas-tight seal for the shaft 206i. Supported within the casing 200 onthe shaft 206 is a rotor 207. The rotor is provided with a perforatedcylindrical outer Wall 208 and a perforated cylindrical inner wall 209.The space between the walls 208 and 209 is divided into sections 210 bypartitions 211. The sections are filled as in the embodiment of FIGS.1-5 by fibrous heat exchange material such as Fiberfrax A cover plate212 and a floor plate 213 are provided for the rotor. The edges of thefloor and cover plates 212 and 213 are finished with sealing .surfaces214 and 215 which cooperate closely with similar surfaces 216 and 217 onthe cover 203 and floor 204 of the casing 200. Extending downwardly fromthe cover 203 of the casing 200 is a sealing member 218. This sealingmember has four vanes 219, 220, 221, and 222, each of which is providedwith a sealing shoe 223. The sealing shoes 223 are each at least as wideas the narrow end of sections 210. The casing 200 is further providedwith vertical sealing legs 224, 225, 226, and 227. 'Ihese legs extendinwardly from the casing and each is terminated wlth a sealing shoe 228which cooperates closely with the outer wall 208 of the rotor 207 tominimize leakage across the face of the sealing shoes.

A duct 229 `is provided in cover 203 for supplying fluid to thecompartment 230 between vanes 219 and 222. A duct 231 is provided Aincover 203 for removing uid from compartment 232 between vanes 222 and221. A duct 233 is provided through cover 203 for supplying fluid tocompartment 234 between vanes 220 and 221. A duct 235 1s providedthrough cover 203 for supplying iiuid to compartment 236 between vanes219 and 220. Duets 237 and 230 are provided through the casing 200 forfurnishing an innocuous sealing uid to the spaces between legs 224 and225; and 226 and 227, respectively.

In operation, a iiuid to be pyrolysed is introduced through duct 229 andpasses into the space between vanes 219 and 222. lIt flows radiallyoutwardly through the sections of the rotor which are available to it.The brous material within these rotor sections is, at least in part, ata temperature sufficient to cause pyrolysis of the hydrocarbonaceousmaterial. As it emerges from the rotor the partially pyrolysed materialmoves into the space between the rotor and the casing 2001. It thenflows circumferentially through this space around the rotor and is drawninwardly through the adjacent rotor sections into the central chamber232 extending between partitions 222 and 221. From here it liows outthrough duct 231. In its inward passage through the rotor thehydrocarbonaceous material is first further pyrolysed and is then cooledor quenched as it leaves the rotor. The rotor is, of course, constantlyturning during the above described sequence and the sections of therotor upon which pyrolysis residue has been deposited are brought into aposition between the vertical sealing legs 226 and 227.

Steam or like innocuous :gas is changed through yduct 238 and enters thespace between rotors 226 and 227. It then Hows inwardly through therotor section opposite this space, purging the fibrous material ofresidual lgases and carrying them into the compartment 234.

Air or other 'oxygen containing gas is introduced into space 234 throughduct 233. The 'oxygen containing gas then passes radially outwardlythrough the rotor into the space between sealing legs 226` and 225. Asthe oxygen containing `gas passes through the rotor, pyrolysis residueis burned from the fibrous material in the rotor, heating the material.The products of combustion iiow circumferentially through the spacebetween legs 225 and 226 and then radially inwardly through the rotor tocompartment 236, whence they are .exhausted through duct 235.

Depending `on the reaction being conducted it may be desirable tointroduce fuel, e.g. methane, into duct 233 along with the air or Iotheroxygen containing gas. 'Ihe fuel is burned in the compartment 234, or inthe fibrous material and furnishes whatever heat may be necessary beyondthat derived from burning the products of pyrolysis, to raise thefibrous material to the required temperature.

In place of burning a fuel in the rotor, it is obvious a fuel may beburned in an external heater (not shown) and the resulting hot lgasescharged to duct 233.

The steam introduced through duct 238 not only purges residual gasesfrom the fibrous material through which it iiows, but forms a seal,preventing oxygen containing gas and products `of combustion fromcontaminating the pyrolysis products in compartment 227.

Another stream of steam is introduced through duct 237 whence it iiowsinto the space between legs 224 and 225, thence through the rotor intocompartment 230, sealing compartment 230 from compartment 236.

The invention will be further described by the following specificexamples which are given for purposes of illustration only and are notintended in any way to restrict the invention beyond the scope -of theappended claims.

Example I An apparatus is constructed according to FIGS. 1 3, the volume:of chamber 44 being such that the residence time at conversiontemperature is about 0.005 second. The rotor has an inner diameter ofinches, an outer diameter of 20 in., and a height =of 11 inches. Intothe annular space provided by this rotor are packed 150 lbs. lofFiberfrax yarn in the form of a porous cloth. The apparatus is rotatedat about 40 r.p.rn. To start the operation a mixture of air and fuel gasis introduced through duct 42, and additional fuel gas through nozzles47. When the average temperature of the inner zone `of the Fiberfraxreaches about 2300c1 F., 300 lbs./ hour of natural gas at about 1atmosphere are introduced through duct 40. The products of pyrolysisremoved through duct 41 comprise (mol percent):

Acetylene 12.5 Hydrogen 72.5 Methane l2 Other i 3 Example Il Theconditions of Example I are repeated except that natural gas is fed atthe rate of 750 lbs/hour, the average temperature of the matrix is about2000 F. and the residence time is about 0.05 second. Of the natural gasconnected, the `gasiform products are distributed as follows (wt.percent):

Light oils 39 Heavy oils 28 Hydrogen 19 `Other 14 Example III Anapparatus is constructed according to FIGS, 4 and 5 of the drawing. Therotor has an inside diarneter of 20 inches, an outside diameter :of 40inches and a length of l2. It is rotated at a speed of 100 r.p.m. Tostart the unit in operation the rotor is rotated and a mixture #of airand fuel 'gas' is introduced through the duct 101 and ignited in theupper central chamber. When the temperature of the Fiberfrax reachesabout l500 F., S000 lbs/hour of ammonia base waste sulphite liquorhaving a soli-ds content of about 25% is introduced through the pipes112. Fluid product is removed through duct 102. On a dry basis, thisproduct analyzes as follows (mol percent):

SO2 35 NH3 32 Combustibles 1 3 Other 20 Example IV The apparatus :ofFIGS. 6 and 7 is constructed using a rotor having an interior diameterof 20 inches, an exterior diameter of 40 inches, and a height of 12inches. In starting up, the rotor is turned at a speed of 100 r.p.m.Flue gas at a temperature of 1600 F. is introduced through the duct 233.When the Fiberfrax packing has reached a temperature of about l500 F.air at 500 F. is substitued `for the flue gas and when the innertemperature of the matrix has decreased to about 600 F., fuel gas isadded to the air in an amount suicient to maintain the temperaturewithin the matrix at about 1500 F., and 5000 lbs/hour of a 4uel oil,dispersed in 10,000 lbs. steam are introduced through duct 229. Theproducts of pyrolysis removed through line 231 comprise (wt. percent offeed) Ethylene 16 Butadiene 5 VOther gases 15 Light 4oils 8 Tar oils andpitch 48 From a consideration of the foregoing description, it will beevident that the invention provides a simple and convenient method forconverting low value hydrocarbonaceous materials into products havinggreater value. Many variations in the process and apparatus describedwill be obvious to those skilled in the art. For example, although inthe apparatus specifically described, Huid flow through the fibrousmaterial is radial, it can obviously be axial if desired. Moreover,valthough only one inlet for feed is shown in each apparatus, evidentlya plurality of feed inlets maybe employed. Again, air or other oxygencontaining gas may be introduced at a variety of different points to aidin combustion of pyrolysis residue and auxiliary fuel.

What I claim is:

1. A method for pyrolytic conversion which comprises passing fluid-formhydrocarbonaceous material to be converted radially through a firstsection of a rotating annular fibrous mass, said -first section of saidmass having a temperature which increases in the direction of How ofsaid hydrocarbonaceous material from a degree not substantially belowthat at which said hydrocarbonaceous material is introduced to a pointat least equal to that at which said hydrocarbonaceous material ispyrolysed and thereby effecting pyrolysis of said material to give avaporous product and a non-vaporous residue and cooling of said mass,removing said vaporous product from said first section, passing vaporouspyrolysis product through a second section of said annular mass, atleast a portion of said second section having a temperaturesubstantially below that at which said vaporous product becomesunstable, to quench said product, removing the quenched product fromsaid second section, passing an oxygen-containing gas in contact With athird section of said mass to burn oi pyrolysis residue lpreviouslydeposited thereon and to preheat said third section for subsequent`contact with fresh material.

I. A method for pyrolytically converting fluid-form hydiocarbonaceousmaterial which comprises passing said material through a mass of -brousheat exchange material, said mass having a temperature which increasesin the direction of flow of said hydrocarbonaceous material from adegree not substantially below that at which said hydrocarbonaceousmaterial is introduced, to a point at least equal to that at which saidhydrocarbonaceous material is pyrolysed, thereby pyrolysing saidhydrocarbonaceous material to give a vaporous product and a non-vaporousresidue and cooling said mass, and passing the vaporous product throughsaid cooled mass of fibrous heat exchange material to cool it.

3. The method claimed in claim 2 wherein the last named mass of heatexchange material has a temperature which decreases in the direction offlow of said vaporous product from a degree not substantially below the10 pyrolysis temperature of the hydrocarbonaceous material, to a degreenot higher than that at which the vaporous products of pyrolysis willremain substantially stable during passage therethrough.

4. Pyrolysis apparatus comprising a easing having a wall, a rotor insaid casing positioned to rotate about its axis, said rotor comprisingan annular mass of fibrous heat storage material, said rotor dening anannular space between itself and said casing and la central cylindricalspace, first sealing means dividing said outer annular space into afirst portion and a second portion, second sealing means dividing saidcentral cylindrical space into a first portion and a second portion,inlet means in said wall for introducing a iluid into the first portionof said outer space, duct means for withdrawing fluid from the firstportion of said central space, spray means for introducing liquid intothe second portion of said central space, outlet means for withdrawinguid from the second portion of said outer space, and means for rotatingsaid rotor.

References Cited in the tile of this patent UNITED STATES PATENTS1,485,083 Kotzebue et al Feb. 26, 1924 1,691,085 Schwarz Nov'. 13, 19281,756,887 Schwarz Apr. 29, 1930 1,959,467 Fields May 22, 1934 1,960,951Oppenheim May 29, 1934 2,304,398 Campbell Dec. 8, 1942 2,389,378 MarisicNov. 20, 1945 2,563,415 Pennington Aug. 7, 1951 2,616,668 Van Weenan etal Nov. 4, 1952 2,739,928 Thayer Mar. 27, 1956 FOREIGN PATENTS 241,866Great Britain Feb. 25, 1926

1. A METHOD FOR PYROLYTIC CONVERSION WHICH COMPRISES PASSING FLUID-FORMHYDROCARBONACEOUS MATERIAL TO BE CONVERTED RADIALLY THROUGH A FIRSTSECTION OF A ROTATING ANNULAR FIBROUS MASS, SAID FIRST SECTION OF SAIDMASS HAVING A TEMPERATURE WHICH INCREASES IN THE DIRECTION OF FLOW OFSAID HYDROCARBONACEOUS MATERIAL FROM A DEGREE NOT SUBSTANTIALLY BELOWTHAT AT WHICH SAID HYDROCARBONACEOUS MATERIAL IS INTRODUCED TO A POINTAT LEAST EQUAL TO THAT AT WHICH SAID HYDROCARBONACEOUS MATERIAL ISPYROLYSED AND THEREBY EFFECTING PYROLYSIS OF SAID MATERIAL TO GIVE AVAPOROUS PRODUCT AND A NON-VAPOROUS RESIDUE AND COOLING OF SAID MASS,REMOVING SAID VAPOROUS PRODUCT FROM SAID FIRST SECTION, PASSING VAPOROUSPYROLYSIS PRIDUCT THROUGH A SECOND SECTION OF SAID ANNULAR MASS, ATLEAST A PORTION OF SAID SECOND SECTION HAVING A TEMPERATURESUBSTANTIALLY BELOW THAT AT WHICH SAID VAPOROUS PRODUCT BECOMESUNSTABLE, TO QUENCH SAID PRODUCT, REMOVING THE QUENCHED PRODUCT FROMSAID SECOND SECTION, PASSING AN OXYGEN-CONTAINING GAS IN CONTACT WITH ATHIRD SECTION OF SAID MASS TO BURN OFF PYROLYSIS RESIDUE PREVIOUSLYDEPOSITED THEREON AND TO PREHEAT SAID THIRD SECTION FOR SUBSEQUENTEDCONTACT WITH FRESH MATERIAL